Hydrogen iodide manufacturing method and hydrogen iodide manufacturing apparatus

ABSTRACT

A hydrogen iodide manufacturing method which includes a step of producing aqueous solution of hydrogen iodide and sulfuric acid by causing iodine-containing aqueous solution and sulfur dioxide to react with each other in a pressurized condition. The pressurized condition may be of not lower than 0.1 MPa in gauge pressure. The method may further include: a separation step of adding iodine to the aqueous solution of hydrogen iodide and separating an upper phase containing sulfuric acid relatively to a large extent and a lower phase containing hydrogen iodide relatively to a large extent; and a step of producing hydrogen iodide by adding sulfur dioxide to the upper phase in a pressurized condition and extracting the produced hydrogen iodide to the lower phase.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application is a divisional of Ser. No. 11/458,537 filedJul. 19, 2006, allowed and the present invention contains subject matterrelated to Japanese Patent Application No. 2005-213111, filed in theJapanese Patent Office on Jul. 22, 2005, the entire content of which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to a hydrogen iodide manufacturing method to beused for manufacturing hydrogen by way of a thermochemical decompositionprocess (IS method: iodine-sulfur method) and an apparatus to be usedfor such a method.

In recent years, the use of hydrogen is attracting attention as fuelthat can suppress the emission of carbon dioxide (CO₂) that is agreenhouse gas. The IS method is known as a technique of manufacturinghydrogen (See, for example, Japanese Patent Publication Nos. 60-52081,60-48442 and 4-37002, and U.S. Pat. No. 4,127,644).

The principal reactions of the IS method include three reactionsexpressed by reaction formulas (1) through (3) shown below. Firstly,water, iodine and sulfur dioxide are made to react with each other at 70to 100 degrees Celsius to produce hydrogen iodide to be used as rawmaterial for forming hydrogen. Although sulfuric acid is also producedat this time, hydrogen iodide and sulfuric acid can be separated fromeach other by extracting the produced hydrogen iodide, using iodine byan amount of two to three times of the mass of the hydrogen iodide. Inthe second step, the obtained hydrogen iodide is thermally decomposed at400 degrees Celsius to obtain hydrogen. In the third step, sulfuric acidis thermally decomposed at a high temperature of 900 degrees Celsius torecover the sulfur dioxide. Since iodine is obtained by thermallydecomposing hydrogen iodide, it is reused with sulfur dioxide. The ISmethod is also referred to as thermochemical decomposition method,because water is decomposed into hydrogen and oxygen by means of sulfurdioxide, iodine and thermal energy by this method.I₂+SO₂+2H₂O→2HI+H₂SO₄  (1)2HI→H₂+I₂  (2)2H₂SO₄→2SO₂+2H₂O+O₂  (3)

The hydrogen iodide forming reaction of the reaction formula (1) is alsoreferred to as Bunsen reaction. The efficiency of forming hydrogeniodide in the Bunsen reaction influences the downstream reactions anddominates the efficiency of hydrogen formation. The hydrogen iodideproduced from the Bunsen reaction is extracted by excessively applyingiodine, and is subsequently condensed by electrodialysis or distillationto form aqueous solution of hydrogen iodide that is concentrated beyondthe azeotropic composition thereof. Hydrogen iodide gas can be obtainedwith ease by distillation from aqueous solution of hydrogen iodide whoseconcentration exceeds the azeotropic composition.

Hydrogen iodide gas is decomposed into hydrogen and iodine according tothe reaction formula (2). The decomposing reaction of hydrogen iodide(Bodenstein reaction) is a uniform gas phase reaction. In the hydrogeniodide decomposing reaction, hydrogen iodide is dissociated to producehydrogen and iodine at or near 400 degrees Celsius, so that hydrogeniodide, hydrogen and iodine coexist as mixed equilibrium gas at thattemperature. The pressure equilibrium constant of the gas has beendetermined to be about 50 and the dissociation ratio is 22%. Therefore,it is important for the hydrogen manufacturing process to raise thehydrogen iodide forming ratio and obtain aqueous solution of hydrogeniodide beyond the azeotropic composition in the hydrogen iodide formingreaction.

While sulfurous acid and iodine quantitatively react with each otherinstantaneously, sulfur dioxide and iodine react with each other only byseveral percent stoichiometrically. The reason for this is that water isrequired for the reaction of sulfur dioxide and iodine, and that sulfurdioxide reacts with iodine only when it is dissolved in water to changeitself into sulfurous acid. The equilibrium constant of the reaction ofdissolving sulfur dioxide in water is 0.054. In view of this numericalvalue, the data is reasonable that the reaction of dissolving sulfurdioxide in water proceeds only by 8% at 55 degrees Celsius and only by4% at 80 degrees Celsius relative to the reaction of sulfurous acid andiodine.

Additionally, while sulfur dioxide is a linear molecule and does nothave any dipole moment, the sulfur atom in sulfurous acid iselectrically positively charged. Therefore, the sulfur atom can easilyinteract with hydrogen iodide when sulfur dioxide is dissolved intowater and turned to sulfurous acid. The reaction of sulfur dioxide,iodine and water proceeds faster at 55 degrees Celsius than at 80degrees Celsius, because sulfur dioxide is dissolved less into waterwhen the temperature is high, and because the reaction efficiency fallsat 80 degrees Celsius due to iodine sublimation at that temperature.

When iodide ions exist in an aqueous solution system, iodine and iodideions form a sort of complex to become more dissolved in water. As theiodine ion concentration rises, the iodine molecule grows to become I₉ ⁻at largest.I₂+I⁻→I₃ ⁻  (5)2I₂+I⁻→I₅ ⁻  (6)3I₂+I⁻→I₇ ⁻  (7)4I₂+I⁻→I₉ ⁻  (8)

Hydrogen iodide and sulfuric acid in the solution produced as a resultof the Bunsen reaction are separated into two phases because of thedifference of density as a result of addition of iodine. Iodide ions andiodine show affinity for each other, and it is known that associationsas expressed by formulas (5) through (8) below take place when theycoexist. The formation constants of the formulas are known. Theformation constants for forming iodide ions/iodine complexes in aqueoussolution of sodium iodide are listed below. Note, however, that β₃ andβ₄ are estimated from the difference between β₁ and β₂ because no datais available about their values.

$\begin{matrix}\begin{matrix}{{\log( \frac{\beta_{1}}{{mol}^{- 1}{dm}^{3}} )} = {\log( \frac{\frac{\lbrack I_{3}^{-} \rbrack}{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}}{{mol}^{- 1}{dm}^{3}} )}} \\{= 2.86}\end{matrix} & ( {9\text{-}1} ) \\\begin{matrix}{{\log( \frac{\beta_{2}}{{mol}^{- 2}{dm}^{6}} )} = {\log( \frac{\frac{\lbrack I_{5}^{-} \rbrack}{{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{2}}}{{mol}^{- 2}{dm}^{6}} )}} \\{= 5.27}\end{matrix} & ( {10\text{-}1} ) \\\begin{matrix}{{\log( \frac{\beta_{3}}{{mol}^{- 3}{dm}^{9}} )} = {\log( \frac{\frac{\lbrack I_{7}^{-} \rbrack}{{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{3}}}{{mol}^{- 3}{dm}^{9}} )}} \\{= 7.23}\end{matrix} & ( {11\text{-}1} ) \\\begin{matrix}{{\log( \frac{\beta_{4}}{{mol}^{- 4}{dm}^{12}} )} = {\log( \frac{\frac{\lbrack I_{9}^{-} \rbrack}{{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{4}}}{{mol}^{- 4}{dm}^{12}} )}} \\{= 8.75}\end{matrix} & ( {12\text{-}1} )\end{matrix}$

The total iodide ion concentration C_(I) ⁻ can be expressed by formula(13) below, and formulas (14) through (18) are obtained from C_(I) ⁻ andthe total equilibrium constants.C _(I) ⁻ =[I⁻]+[I₃ ⁻]+[I₅ ⁻]+[I₇ ⁻]+[I₉ ⁻]  (13)

Thus, formula (9-2) below is obtained from the Formula (9-1).

$\begin{matrix}{{\lbrack I_{3}^{-} \rbrack = {{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}\beta_{1}}}{{Formula}\mspace{14mu}( {10\text{-}2} )\mspace{14mu}{below}\mspace{14mu}{is}\mspace{14mu}{obtained}\mspace{14mu}{from}\mspace{14mu}{the}\mspace{14mu}{formula}\mspace{14mu}{( {10\text{-}1} ).}}} & ( {9\text{-}2} ) \\{{\lbrack I_{5}^{-} \rbrack = {{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{2}\beta_{2}}}{{Formula}\mspace{14mu}( {11\text{-}2} )\mspace{14mu}{below}\mspace{14mu}{is}\mspace{14mu}{obtained}\mspace{14mu}{from}\mspace{14mu}{the}\mspace{14mu}{formula}\mspace{14mu}{( {11\text{-}1} ).}}} & ( {10\text{-}2} ) \\{{\lbrack I_{7}^{-} \rbrack = {{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{3}\beta_{3}}}{{Formula}\mspace{14mu}( {12\text{-}2} )\mspace{14mu}{below}\mspace{14mu}{is}\mspace{14mu}{obtained}\mspace{14mu}{from}\mspace{14mu}{the}\mspace{14mu}{formula}\mspace{14mu}{( {12\text{-}1} ).}}} & ( {11\text{-}2} ) \\{\mspace{79mu}{{\lbrack I_{9}^{-} \rbrack = {{\lbrack I^{-} \rbrack\lbrack I_{2} \rbrack}^{4}\beta_{4}}}\mspace{79mu}{{Thus},}}} & ( {12\text{-}2} ) \\\begin{matrix}{\mspace{79mu}{\alpha_{0} = \frac{\lbrack I^{-} \rbrack}{C_{I^{-}}}}} \\{= \frac{1}{( {1 + {\lbrack I_{2} \rbrack\beta_{1}} + {\lbrack I_{2} \rbrack^{2}\beta_{2}} + {\lbrack I_{2} \rbrack^{3}\beta_{3}} + {\lbrack I_{2} \rbrack^{4}\beta_{4}}} )}}\end{matrix} & (14) \\\begin{matrix}{\mspace{79mu}{\alpha_{1} = \frac{\lbrack I_{3}^{-} \rbrack}{C_{I^{-}}}}} \\{= \frac{\lbrack I_{2} \rbrack\beta_{1}}{( {1 + {\lbrack I_{2} \rbrack\beta_{1}} + {\lbrack I_{2} \rbrack^{2}\beta_{2}} + {\lbrack I_{2} \rbrack^{3}\beta_{3}} + {\lbrack I_{2} \rbrack^{4}\beta_{4}}} )}}\end{matrix} & (15) \\\begin{matrix}{\mspace{79mu}{\alpha_{2} = \frac{\lbrack I_{5}^{-} \rbrack}{C_{I^{-}}}}} \\{= \frac{\lbrack I_{2} \rbrack^{2}\beta_{2}}{( {1 + {\lbrack I_{2} \rbrack\beta_{1}} + {\lbrack I_{2} \rbrack^{2}\beta_{2}} + {\lbrack I_{2} \rbrack^{3}\beta_{3}} + {\lbrack I_{2} \rbrack^{4}\beta_{4}}} )}}\end{matrix} & (16) \\\begin{matrix}{\mspace{79mu}{\alpha_{3} = \frac{\lbrack I_{7}^{-} \rbrack}{C_{I^{-}}}}} \\{= \frac{\lbrack I_{2} \rbrack^{3}\beta_{3}}{( {1 + {\lbrack I_{2} \rbrack\beta_{1}} + {\lbrack I_{2} \rbrack^{2}\beta_{2}} + {\lbrack I_{2} \rbrack^{3}\beta_{3}} + {\lbrack I_{2} \rbrack^{4}\beta_{4}}} )}}\end{matrix} & (17) \\\begin{matrix}{\mspace{79mu}{\alpha_{4} = \frac{\lbrack I_{9}^{-} \rbrack}{C_{I^{-}}}}} \\{= \frac{\lbrack I_{2} \rbrack^{4}\beta_{4}}{( {1 + {\lbrack I_{2} \rbrack\beta_{1}} + {\lbrack I_{2} \rbrack^{2}\beta_{2}} + {\lbrack I_{2} \rbrack^{3}\beta_{3}} + {\lbrack I_{2} \rbrack^{4}\beta_{4}}} )}}\end{matrix} & (18)\end{matrix}$

Thus, α₀ through α₄ show the distribution of formation of the respectiveiodide ions/iodine complexes. From the distribution of formation curves,it is understood that iodide ions and iodine can readily interact andform complexes. Where free [I₂] shows a large proportion, iodide ionsare bonded to iodine to form complexes of higher orders. Therefore,hydrogen iodide is stably bonded to iodine in the lower phase of HI/I₂that is produced as a result of a two-phase separation process. Theyield of iodide ions rises under the condition of little water, probablybecause the iodine concentration relatively rises to form complexes ofhigher orders, which then move to the lower phase.

To obtain gaseous hydrogen iodide by means of the prior art, hydrogeniodide and sulfuric acid are subjected to a two-phase separation processthat uses iodine after the completion of a Bunsen reaction, andsubsequently the lower phase liquid is moved to a hydrogen iodiderefining process so as to remove the sulfuric acid contained in thelower phase liquid by causing a Bunsen reaction to take place in theopposite direction. In this stage of operation, the weight percentconcentration of hydrogen iodide (=(mass of hydrogen iodide contained inlower phase liquid)/(sum of mass of hydrogen iodide and water containedin lower phase liquid)) cannot exceed the azeotropic composition ofhydrogen iodide. Then, it is not possible to directly take out hydrogeniodide anhydride gas with ease. Therefore, the liquid product thatcontains hydrogen iodide is condensed by electrodialysis until it comesto exceed the azeotropic composition. The azeotropic composition ofhydrogen iodide is 57%.

Hydrogen iodide can be isolated with ease from aqueous solution ofhydrogen iodide that is condensed beyond the azeotropic composition bymeans of electrodialysis. Therefore, it is possible to take out purehydrogen iodide gas by distillation in the next step. If the hydrogeniodide concentration in the lower phase liquid can be made to exceed theazeotropic composition as a result of a two-phase separation processthat is conducted after the completion of a Bunsen reaction, theconcentration step of electrodialysis is not necessary.

Sulfur dioxide dissolves by only 0.8 moles in 1 liter of water under theconditions of room temperature and atmospheric pressure, and free sulfurdioxide reacts with water and become decomposed to produce sulfur. Oneof the factors that lower the hydrogen iodide forming efficiency isclogging of pipes due to deposited sulfur. The efficiency of hydrogeniodide formation rises when sulfur dioxide is forcibly mixed with waterthat operates as solvent to increase the contact time with iodine andthe rise of the efficiency of hydrogen iodide formation is reflected tothe efficiency of forming hydrogen. However, once the solubility ofsulfur dioxide in water is exceeded, sulfur dioxide is no longerdissolved in water and free sulfur dioxide reacts with water and becomesdecomposed to produce sulfur, which by turn clogs the pipes of themixer. Additionally, since the reaction of forming hydrogen iodide isconducted at or near 100 degrees Celsius, loss of iodide due tosublimation and clogging of pipes are problems that need to be solved inthe industry.

Since hydrogen iodide can be obtained with ease by causing iodine toreact with aqueous solution of sulfurous acid and an oxidation/reductionreaction to take place, the object of the present invention is to raisethe conversion ratio of sulfur dioxide into hydrogen iodide or sulfuricacid, and thereby to obtain highly concentrated aqueous solution ofhydrogen iodide by improving the solubility of sulfur dioxide relativeto water in a hydrogen iodide forming reaction.

BRIEF SUMMARY OF THE INVENTION

In order to attain the object, according to an aspect of the presentinvention, there is provided a hydrogen iodide manufacturing methodcomprising a step of producing aqueous solution of hydrogen iodide andsulfuric acid by causing iodine-containing aqueous solution and sulfurdioxide to react with each other in a pressurized condition.

According to another aspect of the present invention, there is provideda hydrogen iodide manufacturing method comprising a step of producingsulfuric acid and aqueous solution of hydrogen iodide by: forming afirst aqueous solution containing sulfur dioxide or sulfurous acid byadding sulfur dioxide to water in a pressurized condition; and mixing asecond aqueous solution containing iodine and the first aqueous solutionin a pressurized condition.

According to yet another aspect of the present invention, there isprovided a hydrogen iodide manufacturing apparatus for producinghydrogen iodide and sulfuric acid by causing iodine, sulfur dioxide andwater to react with each other, the apparatus comprising: a sulfurdioxide dissolving tank that is a pressure-resistant container forproducing aqueous solution of sulfur dioxide by mixing sulfur dioxideand water; a sulfur dioxide source for supplying pressurized sulfurdioxide into the sulfur dioxide dissolving tank; a reaction tank that isa pressure-resistant container for causing the reaction to take place ina pressurized condition; a pipe for supplying the aqueous solution ofsulfur dioxide produced in the sulfur dioxide dissolving tank into thereaction tank; iodine-containing aqueous source for supplyingiodine-containing aqueous solution into the reaction tank; and at leastone back pressure valve for discharging gas therethrough from the sulfurdioxide dissolving tank and the reaction tank, so as to maintainpressure in the sulfur dioxide dissolving tank and the reaction tankabove a predetermined level above the atmospheric pressure.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages of the present inventionwill become apparent from the discussion hereinbelow of specific,illustrative embodiments thereof presented in conjunction with theaccompanying drawings, in which:

FIG. 1 is a flowchart of the first embodiment of hydrogen iodidemanufacturing method according to the present invention;

FIG. 2 is a graph illustrating the pressure dependency of the SO₂conversion ratio in the Bunsen reaction;

FIG. 3 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the second embodiment of hydrogen iodidemanufacturing method according to the present invention;

FIG. 4 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the third and fifth embodiments ofhydrogen iodide manufacturing method according to the present invention;

FIG. 5 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the fourth embodiment of hydrogen iodidemanufacturing method according to the present invention; and

FIG. 6 is a graph illustrating the pressure dependency of theconcentration of hydrogen iodide in the lower phase liquid formed by thepressurized Bunsen reaction.

DETAILED DESCRIPTION OF THE INVENTION

Now, the present invention will be described in greater detail byreferring to the accompanying drawings that illustrate preferredembodiments of the present invention.

First Embodiment

FIG. 1 is a flowchart of the first embodiment of hydrogen iodidemanufacturing method according to the present invention. The flow of theembodiment of hydrogen iodide manufacturing method proceeds in a manneras described below.

(1) Sulfur dioxide (SO₂) is supplied to aqueous solution of iodine undera pressurized condition.

(2) Iodine, water and sulfur dioxide react with each other under apressurized condition (Bunsen reaction).

(3) Iodine and water are added to the formation liquid under apressurized condition for two-phase separation to produce an upper phaseand a lower phase, and the Bunsen reaction is caused to take place byfurther adding sulfur dioxide to take hydrogen iodide into the lowerphase and to concentrate the hydrogen iodide beyond the azeotropiccomposition.

(4) After the concentration step of (3) described above, the sulfuricacid in the upper phase liquid is moved to a sulfuric acid decompositionstep.

(5) After the concentration step of (3) described above, the hydrogeniodide in the lower phase liquid is moved to a hydrogen iodidedistillation step.

As sulfur dioxide is pressurized and added to aqueous solution ofiodine, sulfur dioxide is dissolved in water beyond the solubility ofsulfur dioxide to water under the atmospheric pressure, and is caused toquantitatively react with iodine instantaneously to form hydrogen iodideand sulfuric acid. Iodine is added to the formation liquid excessivelyby more than the mass of the produced hydrogen iodide for two-phaseseparation. Then, water and sulfur dioxide are added under a pressurizedcondition to move the sulfuric acid and the hydrogen iodide formed bythe Bunsen reaction, respectively into the upper phase and the lowerphase for concentration.

FIG. 2 is a graph obtained by plotting the conversion ratio of thesulfur dioxide for forming hydrogen iodide and sulfuric acid by way of areaction with iodine when the sulfur dioxide gas has passed through theaqueous solution of iodine, against gauge pressure. The conversion ratioof sulfur dioxide is determined a half of the mass of the hydrogeniodide or the mass of the sulfuric acid formed according to the reactionformula (1) divided by the mass of the added sulfur dioxide. Theconversion ratio shows the ratio of the sulfur dioxide that has reacted.

The solubility of sulfur dioxide under the atmospheric pressure is 5 to10% in terms of weight percentage concentration and the conversion ratiois about 8%, when the gauge pressure is 0 MPa (or atmospheric pressure).This result substantially matches the solubility of sulfur dioxide underthe atmospheric pressure. The conversion ratio of sulfur dioxideincreases in proportion to the gauge pressure up to 0.2 MPa and all theadded sulfur dioxide reacts and the conversion ratio gets to 100% above0.2 MPa. Thus, it will be understood that the conversion ratio risesremarkably when the pressure is raised.

FIG. 6 is a graph illustrating the measured pressure dependency of theconcentration of hydrogen iodide in the lower phase liquid formed by thepressurized Bunsen reaction. When the gauge pressure was 0 MPa (or atthe atmospheric pressure), the concentration of hydrogen iodide in thelower phase liquid was 34% and did not exceed 57% that is theconcentration of the azeotropic composition thereof. However, underpressurized condition of 0.1 MPa or higher pressure, the concentrationof hydrogen iodide in the lower phase liquid exceeded 57% or theconcentration of the azeotropic composition. If the concentration ofhydrogen iodide in the lower phase liquid exceeded the concentration ofthe azeotropic composition, it is easy to separate hydrogen iodide fromthe lower phase liquid in the downstream distillation process. Thus itis understood that efficiency of concentration of hydrogen iodide in thelower phase liquid is enhanced by pressurization.

Sulfur dioxide dissolves in water under pressure and becomes hydrated,so that an oxidation/reduction reaction takes place instantaneouslybetween the sulfur dioxide and the dissolved iodine to produce hydrogeniodide and sulfuric acid. While the ratio of the oxidation/reductionreaction between hydrated sulfur dioxide and iodine is about 8% underthe atmospheric pressure, it can be raised to 100% by adding sulfurdioxide to aqueous solution of iodine under pressure.

Second Embodiment

FIG. 3 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the second embodiment of hydrogen iodidemanufacturing method according to the present invention.

Referring to FIG. 3, a reaction tank 10 is a pressure-resistantcontainer that is provided with a pressure gauge 7 for detecting theinternal gauge pressure of the reaction tank 10. A heater 3 is providedto heat the inside of the reaction tank 10. The reaction tank 10 isequipped with an upper discharge pipe 14 a and a lower discharge pipe 14b. A supply tank 12 is arranged above the reaction tank 10 to supplyiodine and water into the reaction tank 10 by way of a pipe 6.

A sulfur dioxide gas cylinder 1 and a nitrogen gas cylinder 2 arearranged at the outside of the reaction tank 10 to respectively feedsulfur dioxide and nitrogen to the reaction tank 10 by way of respectivemass flow meters 4, a valve 5, a pressurizing pump 11 and a sulfurdioxide feed pipe 25. The sulfur dioxide feed pipe 25 enters thereaction tank 10 from the top of the reaction tank 10 and its lower endis extended to a lower part of the reaction tank 10. The sulfur dioxidegas cylinder 1 is equipped with a heater 3 a.

An exhaust pipe 20 is connected to an upper part of the reaction tank 10and also to an alkali vessel 9 by way of a back pressure valve 8. Thealkali vessel 9 typically contains aqueous solution of sodium hydroxideso as to absorb and collect excessive acid that comes out from theinside of the reaction tank 10 by way of the exhaust pipe 20. Anatmosphere-exposed pipe 21 is connected to an upper part of the alkalivessel 9 to expose the inside of the alkali vessel to the atmosphere.

The reaction tank 10 is provided with water and iodine in advance by wayof the supply tank 12 and the pipe 6. The sulfur dioxide in the sulfurdioxide gas cylinder 1 is heated to 30 to 50 degrees Celsius by theheater 3 a and fed into the reaction tank 10. In this situation, thesupply of sulfur dioxide is regulated and controlled by means of thepressurizing pump 11 and the back pressure valve 8, so that the internalgauge pressure of the reaction tank 10 is not less than 0.1 MPaaccording to reading of the pressure gauge 7. Subsequently, water andiodine are supplied to the reaction tank 10 by way of the supply tank 12and the pipe 6.

Thus, with this embodiment, it is possible to dissolve sulfur dioxideinto the aqueous solution in the reaction tank 10 as sulfur dioxide issupplied into the reaction tank 10 under pressure not lower than 0.1 MPaby operating the pressurizing pump 11 and/or the back pressure valve 8.The dissolved sulfur dioxide hydrates, and it can quantitatively reactwith iodine instantaneously to produce hydrogen iodide and sulfuricacid. The hydrogen iodide and the sulfuric acid that are produced inthis way are separated into a lower phase and an upper phase,respectively. Thus, they can be taken out from the reaction tank 10 byway of the lower discharge pipe 14 b and the upper discharge pipe 14 a,respectively.

Thus, with this embodiment, sulfur dioxide is pressurized and isdissolved into a solvent, which is water. Thus, it is possible to avoidformation of sulfur as a result of reaction of sulfur dioxide and water,and to cause all the supplied sulfur dioxide to react with iodine. Assulfur dioxide is dissolved, it is possible to cause sulfur dioxide toinstantaneously react at room temperature, and hence it is not necessaryto keep the entire reaction tank 10 warm. Thus, it is possible to avoiddeposition of sulfur, and, at the same time, to prevent loss of iodineand clogging of the pipes due to sublimation of iodine.

Third Embodiment

FIG. 4 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the third embodiment of hydrogen iodidemanufacturing method according to the present invention. In FIG. 4, thecomponents same as or similar to those of the second embodiment aredenoted respectively by the same reference symbols and will not bedescribed repeatedly.

With this embodiment, a sulfur dioxide dissolving tank 15 is provided inaddition to the reaction tank 10. Thus, it is so arranged that aqueoussolution of sulfur dioxide that is formed in the sulfur dioxidedissolving tank 15 is transferred to the reaction tank 10 by way of thefeed pipe 6 and a feed valve 22.

The sulfur dioxide dissolving tank 15 is a pressure-resistant containerthat is provided with a pressure gauge 7 for detecting the internalgauge pressure of the sulfur dioxide dissolving tank 15. A heater 3 isprovided to heat the inside of the sulfur dioxide dissolving tank 15.

A sulfur dioxide gas cylinder 1 and a nitrogen gas cylinder 2 arearranged at the outside of the sulfur dioxide dissolving tank 15 and thereaction tank 10 to feed sulfur dioxide and nitrogen, respectively, tothe sulfur dioxide dissolving tank 15 by way of respective mass flowmeters 4, a valve 5, a pressurizing pump 11 and a sulfur dioxide feedpipe 25.

An exhaust pipe 20 is connected to an upper part of the sulfur dioxidedissolving tank 15 and also to an alkali vessel 9 by way of a backpressure valve 8. An atmosphere-exposed pipe 21 is connected to an upperpart of the alkali vessel 9 to expose the inside of the alkali vessel 9to the atmosphere.

The reaction tank 10 is equipped with an upper discharge pipe 14 a and alower discharge pipe 14 b. A supply tank 12 is arranged above thereaction tank 10 to supply iodine and water into the reaction tank 10 byway of the pipe 6.

The sulfur dioxide in the sulfur dioxide gas cylinder 1 is heated to 30to 50 degrees Celsius by the heater 3 a and is fed into the sulfurdioxide dissolving tank 15. In this situation, the supply of sulfurdioxide is regulated and controlled by means of the pressurizing pump 11and the back pressure valve 8, so that the internal gauge pressure ofthe sulfur dioxide dissolving tank 15 is not less than 0.1 MPa accordingto reading of the pressure gauge 7. The sulfur dioxide dissolving tank15 is provided with water in advance. Alternatively, water may besupplied to the sulfur dioxide dissolving tank 15 from a supply pipe 13.The aqueous solution of sulfur dioxide that is formed in the sulfurdioxide dissolving tank 15 is held in a pressurized state and is movedinto the reaction tank 10. The reaction tank 10 is provided with iodineor aqueous solution of iodine in advance. The inside of the reactiontank 10 is also regulated and controlled by means a back pressure valve8 a, so that the internal gauge pressure of the reaction tank 10 is keptnot less than 0.1 MPa.

Thus, with this embodiment, sulfur dioxide is dissolved into the waterin the sulfur dioxide dissolving tank 15 to produce a highlyconcentrated aqueous solution of sulfur dioxide by regulating theinternal gauge pressure of the sulfur dioxide dissolving tank 15 to notlower than 0.1 MPa by means of the pressurizing pump 11 and/or the backpressure valve 8. Additionally, the aqueous solution of sulfur dioxideis transferred into the reaction tank 10, while maintaining thepressurized condition thereof, to cause it to react with iodine toproduce hydrogen iodide and sulfuric acid.

Sulfur dioxide is dissolved in water, and hydrates with water moleculesto be chemically changed into sulfurous acid molecules as shown inFormula (4-1). Sulfurous acid is reducing and reacts immediately withiodine quantitatively.SO₂+H₂O→H₂SO₃  (4-1)SO₂+nH₂O→SO₂.nH₂O  (4-2)

Therefore, if sulfur dioxide is dissolved in water and is changed intosulfurous acid molecules or into hydrated sulfur dioxide molecules asshown in Formula (4-2) in advance, almost all the sulfur dioxide addedto the reaction system can be reacted. With such a process, quantity ofthe formed hydrogen iodide is larger and the reaction efficiency ishigher, compared with a process causing sulfur dioxide to react withiodine while passing sulfur dioxide through water.

In addition, when sulfur dioxide passes through water, excess sulfurdioxide reacts with water, and sulfur is formed as a result of a sidereaction shown in the following formula:3SO₂+2H₂O→2H₂SO₃+S

Thus, as sulfur dioxide is dissolved into water under pressure in thesulfur dioxide dissolving tank 15, it is possible to produce highlyconcentrated aqueous solution of, sulfurous acid, which is then causedto react with iodine in the reaction tank 10 to produce highlyconcentrated hydrogen iodide. While it is not possible to dissolvesulfur dioxide into water by more than 5% in terms of weight percentageconcentration under the atmospheric pressure, it is possible to produceaqueous solution of sulfur dioxide with a concentration not lower than80% by pressurizing sulfur dioxide and cause it to quantitatively reactwith iodine instantaneously. As the operation of dissolving sulfurdioxide into water and that of causing the aqueous solution of sulfurdioxide to react with iodine under a pressurized condition areconducted, it is possible to avoid a decomposition reaction of sulfurdioxide by water and hence no sulfur deposition takes place.

Fourth Embodiment

FIG. 5 is a schematic diagram of a hydrogen iodide manufacturingapparatus that can be used for the fourth embodiment of hydrogen iodidemanufacturing method according to the present invention. In FIG. 5, thecomponents same as or similar to those of first through thirdembodiments are denoted respectively by the same reference symbols andwill not be described repeatedly.

While the hydrogen iodide manufacturing apparatus of FIG. 5 has aconfiguration similar to that of FIG. 3, it differs from the latter inthat the lower end of the sulfur dioxide feed pipe 25 in the reactiontank 10 is located slightly below the liquid surface in the reactiontank 10 and hence considerably above the lower end of the sulfur dioxidefeed pipe 25 of FIG. 3.

With this embodiment, sulfur dioxide is heated to 30 to 50 degreesCelsius by the heater 3 a and is fed into the reaction tank 10. In thissituation, the supply of sulfur dioxide is regulated and controlled bymeans of the pressurizing pump 11 and the back pressure valve 8, so thatthe internal gauge pressure of the reaction tank 10 is not less than 0.1MPa according to reading of the pressure gauge 7. The reaction tank 10is provided with water and iodine in advance. Alternatively, iodine andwater may be supplied from the iodine and water supply tank 12 into thereaction tank 10 by way of the feed pipe 6.

Iodine is added to the aqueous solution that contains hydrogen iodide,formed as a result of the Bunsen reaction, not less than 0.5 times ofthe mass of the hydrogen iodide to produce two phases of an upper phaseand a lower phase. It is preferable that iodine is added by a mass notless than 0.5 times of the mass of the hydrogen iodide, becauseexcessive iodine constantly exists under such a condition. Sulfurdioxide is added to the two-phase liquid under a pressurized conditionof not lower than 0.1 MPa and water and iodine are supplied from thefeed pipe 6 to maintain the two-phase situation.

With this embodiment, iodine is added to the aqueous solution thatcontains hydrogen iodide as produced in the first embodiment or thesecond embodiment to produce a two-phase liquid, and then, sulfurdioxide is added under pressure. The added sulfur dioxide is dissolvedmainly in the upper phase that contains water to a large extent andbecome hydrated to consequently react with the iodine mainly dissolvedin the lower phase and located near the interface of the two-phaseliquid to form hydrogen iodide and sulfuric acid.

As sulfur dioxide is added to the two-phase liquid, while maintaining apressurized state, sulfur dioxide is hydrated in the upper phase, andthe hydrogen iodide formed as a result of the reaction of sulfur dioxideand iodine along the interface of the two-phase liquid is drawn into thelower phase, while sulfuric acid remains in the upper phase. Thus,hydrogen iodide is drawn into the lower phase as it forms a complex withiodine when water and iodine are supplied to the two-phase liquid systemto maintain the two-phase situation, and it becomes concentrated, as itis dehydrated. The Bunsen reaction and the two-phase separation can berealized simultaneously by adding sulfur dioxide, while pressuring it toa gauge pressure level of 0.1 MPa or higher. Then, the hydrogen iodideconcentration in the lower phase can exceed 57% that is theconcentration of the azeotropic composition thereof.

The Bunsen reaction was actually conducted in a pressurized conditionwhen the reading of the pressure gauge 7 was 0.4 MPa, and then hydrogeniodide was condensed while maintaining the two-phase state situation toget to a concentration of 73 to 94% of hydrogen iodide in terms ofweight percentage concentration that was in excess of the azeotropiccomposition thereof. If the aqueous solution of hydrogen iodide in thelower phase is left under the atmospheric pressure, the hydrogen iodideconcentration decreases. However, it is possible to maintain theconcentrated state by producing two phases under pressure andmaintaining the pressurized condition.

Fifth Embodiment

Now, a fifth embodiment of hydrogen iodide manufacturing methodaccording to the present invention will be described below. The hydrogeniodide manufacturing apparatus to be used for this embodiment has aconfiguration same as that of the third embodiment (FIG. 4).

With this embodiment, the sulfur dioxide in the sulfur dioxide gascylinder 1 is heated by the heater 3 a to 30 to 50 degrees Celsius andfed into the sulfur dioxide dissolving tank 15. In this situation, thesupply of sulfur dioxide is regulated and controlled by means of thepressurizing pump 11 and the back pressure valve 8, so that the internalgauge pressure of the sulfur dioxide dissolving tank 15 is not less than0.1 MPa according to reading of the pressure gauge 7. The sulfur dioxidedissolving tank 15 is provided with water in advance. Alternatively,water may be supplied to the sulfur dioxide dissolving tank 15 from asupply pipe 13.

The aqueous solution of sulfur dioxide produced in the sulfur dioxidedissolving tank 15 is then moved to the reaction tank 10 by way of thefeed pipe 6 and the feed valve 22 while maintaining the aqueous solutionof sulfur dioxide in the pressurized condition. The reaction tank 10 isprovided with iodine or aqueous solution of iodine in advance. Theinside of the reaction tank 10 is also regulated and controlled, so thatthe internal gauge pressure of the reaction tank 10 is not less than 0.1MPa. The reaction tank 10 is provided with water and iodine in advance.Iodine is put into the reaction tank 10 by an amount not less than 0.5times of the mass of water. When sulfur dioxide is added by an amountnot less than 0.5 times of the mass of the iodine in the reaction tank10, the reaction solution in the reaction tank 10 is divided into upperand lower phases. The addition of aqueous solution of sulfur dioxide tothe produced two-phase liquid is continued from the sulfur dioxidedissolving tank 15 while it is pressurized to a gauge pressure level notlower than 0.1 MPa. At the same time, water and iodine are supplied fromthe supply tank 12 by way of the feed pipe 6 to maintain the two-phasesituation.

Thus, with this embodiment, the hydrogen iodide and the sulfuric acidproduced by adding sulfur dioxide to iodine-containing aqueous solutionin a pressurized condition form two phase liquid because of iodine thatis present excessively. As sulfur dioxide is added to the formedtwo-phase liquid in a pressurized condition, the added sulfur dioxide isdissolved mainly in the upper phase that contains water to a largeextent so as to be hydrated, and to react with iodine mainly dissolvedin the lower phase along the interface of the two-phase liquid toconsequently produce hydrogen iodide and sulfuric acid.

Thus, with this embodiment, two-phase liquid is formed as the Bunsenreaction proceeds when iodine is added to the reaction tank 10 by anamount not less than 0.5 times of the mass of water. Then, as sulfurdioxide is added to the formed two-phase liquid while maintaining thepressurized condition, sulfur dioxide is hydrated in the upper phase.Then, the hydrogen iodide produced by a reaction of sulfur dioxide withiodine along the interface of the two-phase liquid is drawn into thelower phase. Meanwhile, sulfuric acid remains in the upper phase. Aswater and iodine are supplied to the two-phase liquid system so as tomaintain the two-phase situation, hydrogen iodide forms complex withiodine and is drawn into the lower phase. Then, consequently, hydrogeniodide is dehydrated and the hydrogen iodide becomes concentrated. TheBunsen reaction and the two-phase separation can be realizedsimultaneously by adding sulfur dioxide, while pressurizing to a gaugepressure level of 0.1 MPa or higher. Then, the hydrogen iodideconcentration in the lower phase can exceed 57% that is theconcentration of the azeotropic composition thereof.

The embodiments of the hydrogen iodide manufacturing methods andhydrogen iodide manufacturing apparatus in accordance with the presentinvention explained above are merely examples, and the present inventionis not restricted thereto. It is, therefore, to be understood that,within the scope of the appended claims, the present invention can bepracticed in a manner other than as specifically described herein.

1. A hydrogen iodide manufacturing apparatus for producing hydrogeniodide and sulfuric acid by causing iodine, sulfur dioxide and water toreact with each other, the apparatus comprising: a sulfur dioxidedissolving tank that is a pressure-resistant container for producingaqueous solution of sulfur dioxide by mixing sulfur dioxide and water; asulfur dioxide source for supplying pressurized sulfur dioxide into thesulfur dioxide dissolving tank; a reaction tank that is apressure-resistant container for causing the reaction to take place in apressurized condition; a pipe for supplying the aqueous solution ofsulfur dioxide produced in the sulfur dioxide dissolving tank into thereaction tank; iodine-containing aqueous source for supplyingiodine-containing aqueous solution into the reaction tank; and at leastone back pressure valve for discharging gas therethrough from the sulfurdioxide dissolving tank and the reaction tank, so as to maintainpressure in the sulfur dioxide dissolving tank and the reaction tankabove a predetermined level above the atmospheric pressure.
 2. Theapparatus according to claim 1, wherein the predetermined level abovethe atmospheric pressure is not lower than 0.1 MPa in gauge pressure.